Novel fragrance materials and process

ABSTRACT

A novel ester comprising the reaction product of longifolene and formic acid, perfume and fragrance compositions containing same and process therefor.

United States Patent Wight et al.

[451 Sept. 23, 1975 NOVEL FRAGRANCE MATERIALS AND PROCESS Inventors:Christian F. Wight, Mount Kisco, v

N.Y.; John B. Hall, Rumson, NJ.

International Flavors & Fragrances Inc., New York, N.Y.

Filed: May 29, 1973 Appl. No.: 364,918

Related u.s. Application Data Continuation of Ser. No. 37,333, May I4,1970, abandoned.

Assignee:

US. Cl 260/489; 252/522; 260/497 R Int. Cl. C07C 67/04; CO7C 69/07 Fieldof Search 260/489, 497 R, 488 B References Cited UNITED STATES PATENTS3/1972 Curtis et al. 260/489 Primary Examiner-Vivian Garner.

FOREIGN PATENTS OR APPLICATIONS 1,225,158 3/1971 United Kingdom .i260/488 OTHER PUBLICATIONS Chem. Abstracts, 55:11458a (196] Attorney,Agent, or FirmBrooks Haidt l-laffner & Delahunty [57] ABSTRACT 5 Claims,No Drawings NOVEL FRAGRANCE MATERIALS AND PROCESS This is a continuationof Application Ser. No. 37,333, filed May 14, 1970, now abandoned. Y

The present invention relates in general to perfumery and in particularto the provision of-a novel-substance beneficially adapted for use inconnection with .the preparation of perfume and fragrance compositions.

The use of perfume ingredients in the manufacture of a wide variety ofindustrial products such as soaps, de tergents, deodorants, cosmeticpreparations and the like for purposes of imparting thereto anesthetically pleasing odor characteristic comprises, of course, wellestablished practice. The commercial importance of perfume agents is, ofcourse, to a great extent self evident and especially as regardsapplications primarily cosmetic in nature. However, in many instances,e.g., soaps and detergents manufacture, esthetic rather than functionalconsiderations may well be determinative of product marketability andthus, considerations associated with product appearance, fragrance andthe like assume rather critical importance.

Natural essential oils are widely exploited perfumery agents but haveseveral disadvantages which detract from their commercial desirability.Hence, considerable industrial activity has centered around the researchand development of synthetic perfume agents by suitable derivatizationof natural occurring materials. Occasionally one comes across anabundant low cost essential oil with a major component which can beupgraded via suitable derivatives. One of the important advantages isthe new body of matter is often a single controllable material free oftheunavoidable variations connected with whole natural oils, differingfrom year to year and from lot to lot because they are obtained byvariable primitive techniques. Moreover, a single chemical entity alsoaffords a more predictable performance regarding compatability,stability, uniform fragrance strength and character in the multiplicityof end products in which perfumes are required. When such a derivativehas great power coupled with low cost and a high degree of odor qualityonly obtainable by the use of expensive alternate materials, a valuabletool is presented to the perfumer.

Thus, a primary object of the present invention resides in the provisionof a perfume and fragrance composition wherein certain disadvantages areeliminated and a novel perfume agent of superior functionality isprovided.

Other objects and advantages of the present invention will become moreapparent hereinafter as the description proceeds.

The attainment of the foregoing and related objects is made possible inaccordance with the present invention which in its broader aspectsincludes the provision of a novel perfuming agent, compositionscontaining same .as well as processing therefor and wherein said perfumeagent comprises an ester which is the reaction product of longifoleneand formic acid.

The longifolene-formic acid reaction product provided in accordance withthe present invention posthetically pleasing, provides an aroma of goodintensity, the fragrance characteristics persisting for significantperiods'of time as evidenced by dry-out evaluation.-

' The 'longifolene-formic acid reaction product may be readilyprepared-by contacting at a temperature ranging from about 30C to about90C, longifolene (C H i.e., 1,4-methanoazulene, decahydro-4,8,8-trimethyl-9 methylene, with formic acid in amounts sufficient to yield amole ratio of formic acid to longifolene with the range of about 2 toabout 10, said contacting being preferably carried out in the presenceof an effective amount of a protonic acid such as sulfuric acid or aLewis acid catalyst such as paratoluene sulfonic acid or methanesulfonic acid typified by boron trifluoride etherate, stannic chlorideand the like and for a time sufficient to form the ester derivative; thelatter may thereafter be recovered by any suitable separation technique,e.g., extraction, fractional distillation and the like.

The quantity of Lewis acid or protonic acid catalyst employed is notparticularly critical apart from the requirement that it be present ineffective amounts, i.e., quantities sufficient to permit the desiredreaction rate. Thus, the catalyst component may be present in amountsvarying from a small but effective amount, i.e., on the order of about1% up to about 7% by weight of the formic acid.

The reaction may, if desired, be carried out in the presence of an inertsolvent vehicle including, mobile liquid alkanes, e.g., propane, hexane,octane and the like; liquid aryl hydrocarbons, e.g., benzene, toluene,xylene, etc. However, since solvent materials are of an optional nature,their use is recommended against in order to minimize costs which wouldotherwise accrue in connection with necessary solvent-removaloperations.

As previously indicated, the reaction is preferably carried out at atemperature within the range of from 30C to 90C. Within the.aforestatedv range, specific valueswill be selected having reference tothe reaction rate desired, the latter beinginfluenced by the nature andtype of solvent employed, if any, ratio reactants, amount of catalystandthe like. The temperature selected should not be so high as to result inundesirable side reactions or degradative decomposition of one or moreof the involved ingredients or so low as to cause extended reactiontimes. In general, it is found that optimum results obtain with the useof temperatures within the range of 40C to C, and accordingly, suchrange is particularly preferred for use herein.

Product yield can be improved appreciably by employing a holding periodwith agitation following complete additionof the reactants and catalyst.The length of any such holding period will depend, for example, onreactant ratio, agitation level, etc. In general, holding periodssubstantially in excess of 10 hours will not be required andparticularly in view of the availability of modern, highly efficientprocessing equipment; thus, agitation is desirably carried out forperiods ranging from aboutvone hour to about 6 hours.

The formicacidreactant is preferably employed in molar excess in order-to minimize quantities of unrea'cted longifolene, thereby facilitatingproduct isolation and recovery while diminishing the formation ofundesired by products. Inaccordance with preferred practice, the-formicacid is employed in a molar excess of 2-10 or more times.

Pressure is not particularly critical in the practice of the presentinvention and thus, the reaction can be car.- ried out under eithersubatmospheric or superatmospheric pressure conditions. However, suchmodes of proceeding require the use of specialized equipment which, inaddition to the high cost involved, can prove burdensome from thestandpoint of operation. Accordingly, it is in general preferred toemploy atmospheric pressure.

The product can be recovered from the reaction medium by conventionalmeans including washing, distillation, extraction, preparativechromatography, and the like. Fractional distillation under relativelyhigh vacuum is particularly preferred, being especially conductive toeffective separation and recovery. More specifically, upon completion ofthe desired reaction, it is generally recommended to wash the reactionmixture and to separate the organic layer. The aqueous layer can then beextracted with a suitable organic solvent such as benzene to recover theproduct as well as starting materials present therein. The organicsolutions may then be combined and subjected to vacuum, fractionaldistillation whereby to provide the ester product.

The longifolene reactant employed in the aforedescribed process,comprises a cyclic terpene having the following structural formula:

Longifolene is widely distributed in nature, notably among species ofthe genus Pinus. One of the sources of longifolene is so-called Indianterpentine oil obtained from Pinus [ongifolia Roxb. It occurs in suchIndian terpentine oil in amounts of about 30%, and is preferablypurified before use herein to purities on the order of 80% or more.

The novel fragrance material provided in accordance with the presentinvention can be employed to advantage in a wide variety of applicationsto impart a rich, precious wood fragrance.

As olfactory agents, such material can be formulated into or used as acomponent of a perfume composition. Thus, such material, in addition tohaving an esthetically pleasing fragrance, exhibits excellent stabilityin a wide variety of perfume articles and perfume compositions. Theterminology perfume composition as used in the context of the presentinvention, is intended to encompass a relatively Wide variety ofrelationships. Thus, the composition in question may comprise an ultimate perfume product or alternatively, a fragranceimpartingcomposition adapted to be incorporated into a finished perfume forpurposes of supplying a total fragrance impression or to enhance, modifyor otherwise reinforce the natural fragrance characteristics of suchproduct. Thus, suitable companion fragrance ingredients suitable for usein formulating the compositions comtemplated herein include, forexample, natural and synthetic oils, alcohols including both saturatedand unsaturated alcohols, ketones, esters, lactones, aldehydes, ethers,anthranilates; acetals, terpenes; carboxylic acids, diphenyl compounds,heterocyclic com- 4 pounds including azole s, quinolines, themacrocyclic musks including ketones, polycyclic musks including tetralinmusks. Other ingredients which may be suitable in a particularinstance-include, for example, solvents, dispersants, emulsifiers,surface-active agents, aerosol propellants and the like, depending uponthe specific nature of the product being formulated, e.g., detergent,soap, space deodorant, cologne, bath preparation such as bath oil, bathsalts, hair preparations such as lacquers, brilliantines, pomades andshampoos; cosmetic preparations such as creams, deodorants, handlotions, sun screens; powders such as talcs, dusting powders, facepowder and the like.

. In preparing perfume compositions, the individual componentscontribute their particular olfactory characteristics, but the overalleffect of the perfume compositions will be the sum of the effect of eachingredient. Thus, the ester derivative of the present invention may beused to alter the aroma characteristics of a perfume composition, forexample, by highlighting or moderating the olfactory reactioncontributed by another ingredient of the composition. The term alter asused herein is intended to denote an effect on the fragrance impression,harmoniously blending with the other ingredient'materials to produce anovel bouquet, or alternatively, enhancing, fortifying or reinforcing anexisting fragrance note. I

The amount of ester employed in a particular instance may vary over arelatively wide range and will be determined by a number of factorsincluding, the nature and quantity of other ingredients, as well as theeffects desired to be achieved. In any event, the essential requirementis that the ester reaction product be present in effective quantities,i.e., the amounts sufficient to alter the fragrance of the composition,e.g., carrier or vehicle. Thus, it has been found that perfumecompositions containing a small but effective amount, e.g., as little as2% by weight of the ester derivative, or even less, may be employed toadvantage for purposes of imparting a pleasant wood aroma to soaps,cosmetics and other products. The amount employed can range up to 7% orhigher, depending again upon the nature of the end product, the effectdesired, as well as the particular fragrance sought. It will further beunderstood that the end product carrier or vehicle can be a liquid suchas an alcohol, glycol or the like or alternatively, can be an absorbentsolid such as talc or components for encapsulating the composition.

The following examples are given for purposes of illustration only andare not to be considered as necessarily constituting a limitation on thepresent invention.

EXAMPLE 1 PREPARATION OF LONGIFOLENE-FORMIC ACID REACTION PRODUCT FormicAcid Longifolene (88.7 moles) (40 moles) To the flask contents are added600 g. of boron trifluoride etherate over a period of 15 minutes duringwhich the temperature rises to 35C. The mixture thus ,formed is stirredfor 4 hours at 50C and thereafter added to a receptacle containing 20liters of water and 2 liters of benzene. The aqueous layer is decantedand extracted with 2 liters of benzene. The organic solutions arethereafter bulked and washed three times with 1.5 liters of a saturatedaqueous solution of sodium bicarbonate. The benzene is then stripped offto a pot temperature of 110C., atmospherically, yielding 8748 g. of oil(acid value 1A=nil, ester value lS=4l.2%) containing about 35-40% ofester product. Fractional dis- ;tillation of the crude oil in thepresence of 3% Prime] (refined mineral oil) and 0.1% lonox anti-oxidantat a pressure of 0.4 mm Hg, a reflux ratio of 2:1 and pot temperature of100l30C. through a 12 inch X 44 mm. Goodloe packed column serves toremove lower boiling fractions determined by gas-liquid chromatography(GLC) to constitute essentially isolongifolene, such determination beingconfirmed by nuclear magnetic resonance (NMR). The desired product istherefore obtained by fractionally distilling the residue through a 12inch X 44 mm. Goodloe packed column at a pressure of 0.3-0.7 mm. Hg at areflux ratio of 9:1, (pot temperature l24l84C) and collecting thematerial having a boiling point of 89-92C. Yield: 3187.4

The product has an .ester value of 96.5% and a nil acid value.

A perfume of the following composition is prepared:

The resultant composition provides an interesting variation in the basicclassic cologne blend, i.e., having a woody, amber-like fragrance note.Such fragrance exhibits good persistence on dry-out evaluation.

EXAMPLE 2 To a 2 liter flask fitted with stirrer, thermometer,additional funnel and reflux condenser are charged 480 g. longifoleneand 480 g. of formic acid. To the flask contents 96 cc. of a 50%(v/v)sulfuric acid/water solution is added over a period of 30 minutes withgood stirring. After the exotherm subsides the temperature is raised to50C and the reaction mass stirred at 50C for another 6 hours. Themixture is then poured into 1.5 liters of water and the organic layerseparated. The aqueous layer is extracted with toluene, the combinedorganic layer is washed neutral and the solvent stripped off.Distillation of the residual oil yields 220 g. of isolongifolene and g.of product. (Mainly a mixture of longifolene formates plus somealcohols.)

Perfume compositions similar to that described as Example 1 but preparedwith the longifolene formate of Example 2 have a pleasant, woodyfragrance note and exhibit good persistence on dry-out evaluation Whatis claimed is:

1. A product which is formed by the reaction of longifolene and formicacid, the product being formed by contacting longifolene and formic acidin the presence of sulfuric acid, boron trifluoride etherate, or stannicchloride acid catalyst at a temperature of about 30C to about 90C in amole ratio of formic acid to longifolene within the range of about twoto 10.

2. A process for the preparation of the product of claim 1 whichcomprises contacting at a temperature of between about 30C to about 90Clongifolene with formic acid, in amounts sufficient to yield a moleratio of formic acid to longifolene within the range of about two toabout 10, said contacting being carried out in the presence of sulfuricacid, paratoluene sulfonic acid, methane sulfonic acid, borontrifluoride etherate, or stannic chloride acid catalyst to form saidproduct, and thereafter recovering said product.

3. A process according to claim 2, wherein said catalyst is borontrifluoride ethereate.

4. A process according to claim 2 wherein the catalyst component ispresent in amounts of from about 1 percent up to about 7 percent byweight of the formic acid.

5. A process according to claim 2 wherein the contacting is carried outfrom about one to about 6 hours.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO.3,907,873

DATED September 23 1975 |NVENTOR(S) CHRISTIAN F. WIGHT and JOHN B. HALLIt is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below: 0

Col. 3, line 59, after "perfume" and before "for" insert -producta C01.6, line 6 at the beginning of the line,

"-ditional" should read -dition Signed and Scaled this Q Twentieth Dayof July 1976 [SEAL] Arrest.

0 RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioneroj'Parenrs and Trademarks

1. A PRODUCT WHICH IS FORMED BY THE REACTION OF LONGIFOLENE AND FORMICACID, THE PRODUCT BEING FORMED BY CONTACTING LONGIFOLENE AND FORMIC ACIDIN THE PRESENCE OF SULFURIC ACID, BORON TRIFLUORIDE ETHERATE, OR STANNICCHLORIDE ACID CATALYST AT A TEMPERATURE OF ABOUT 30*C TO ABOUT 90*C IN AMOLE RATIO OF FORMIC ACID TO LONGIFOLENE WITHIN THE RANGE OF ABOUT TWOTO
 10. 2. A process for the preparation of the product of claim 1 whichcomprises contacting at a temperature of between about 30*C to about90*C longifolene with formic acid, in amounts sufficient to yield a moleratio of formic acid to longifolene within the range of about two toabout 10, said contacting being carried out in the presence of sulfuricacid, paratoluene sulfonic acid, methane sulfonic acid, borontrifluoride etherate, or stannic chloride acid catalyst to form saidproduct, and thereafter recovering said product.
 3. A process accordingto claim 2, wherein said catalyst is boron trifluoride ethereate.
 4. Aprocess according to claim 2 wherein the catalyst component is presentin amounts of from about 1 percent up to about 7 percent by weight ofthe formic acid.
 5. A process according to claim 2 wherein thecontacting is carried out from about one to about 6 hours.